US20090176963A1 - Organic-acid-based catalyst for production of polylactic acid - Google Patents

Organic-acid-based catalyst for production of polylactic acid Download PDF

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US20090176963A1
US20090176963A1 US12/308,066 US30806607A US2009176963A1 US 20090176963 A1 US20090176963 A1 US 20090176963A1 US 30806607 A US30806607 A US 30806607A US 2009176963 A1 US2009176963 A1 US 2009176963A1
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acid
organic
catalyst
based catalyst
lactic acid
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Atsushi Abiko
Hisako Iwahashi
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Kyoto Institute of Technology NUC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/06—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing halogen atoms, or nitro or nitroso groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C07D213/18—Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms

Definitions

  • the present invention relates to an organic-acid-based catalyst for direct dehydration polycondensation of hydroxycarboxylic acids, in particular L-lactic acid.
  • Polyhydroxycarboxylic acids such as poly-L-lactic acid, which are superior in mechanical, physical and chemical properties and biodegradable, i.e., decomposed under natural environment by microorganisms finally into water and carbon dioxide gas, are recently attracting attention in various fields, for example, as a medical material and a general-purpose resin substitute, and therefore there is expected large increase in its demands in the future.
  • Poly-L-lactic acid is prepared as described below by ring-opening polymerization of L-lactide, cyclic diester monomer of lactic acid (lactide method) or by indirect polymerization method, for example, via L-lactic acid oligomer (“lactide method” is also included in the indirect polymerization method).
  • the lactide method gives high-molecular weight poly-L-lactic acids as the raw material is purified by isolation of lactide, but industrial lactide production and purification demanded significantly cost increase in operation and facility, causing a problem in producing inexpensive product.
  • Nonpatent Documents 1 to 4 There are only limited kinds of the catalysts used in the indirect polymerization method, and there are reports of using p-toluenesulfonic acid, tin chloride, or tin chloride and p-toluenesulfonic acid in combination as the catalyst (Nonpatent Documents 1 to 4).
  • Nonpatent Document 1 lactic acid is first converted to an oligomer at a catalyst/L-lactic acid ratio of 2.5 wt % and then polymerized by azeotropic dehydration polycondensation by using molecular sieve to a polymer having a molecular weight of about 100,000.
  • Nonpatent Document 2 In the report of the combined use of tin chloride and p-toluenesulfonic acid as a catalyst (Nonpatent Document 2), lactic acid is first converted to an oligomer while heated in the absence of catalyst under reduced pressure and then melt-polymerized in the presence of an added catalyst (catalyst/oligo(L-lactic acid) ratio: 0.4 wt %) to a polymer having a molecular weight of about 20,000, crystallized under heat, and post-polymerized in solid phase to give a polymer having a molecular weight of about 100,000.
  • an added catalyst catalyst/oligo(L-lactic acid) ratio: 0.4 wt %
  • Patent Documents 1-5 Although there are reports of a catalyst for direct polycondensation of lactic acid (Patent Documents 1-5), the methods have many problems in catalytic activity and process configuration such as low stability of the catalyst to water, low catalytic activity, necessity of complete removal of the catalyst because of use of metal catalyst etc., and for that reason, the indirect polymerization method has been used in practice.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2003-335850
  • Patent Document 2 Japanese Patent Application Laid-Open No. 10-231358
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2001-213949
  • Patent Document 4 Japanese Patent Application Laid-Open No. 2002-138142
  • Patent Document 5 Japanese Patent Application Laid-Open No. 2004-43727
  • Nonpatent Document 1 Ajioka M, Enomoto E, Suzuki K and Yamaguchi A, Bull. Chem. Soc. Jpn 1995, 68, 2125.
  • Nonpatent Document 2 S. I. Moon, I. Taniguchi, M. Miyamato, Y. Kimura and C. W. Lee., High Perform. Polymer, 2001, 13, S189-S196.
  • An object of the present invention which was made under the circumstances above, is to provide a new organic-acid-based catalyst that can synthesize poly-L-lactic acid by direct dehydration polycondensation of L-lactic acid.
  • the present invention provides an amine salt or phosphine salt of sulfonic acid as a new organic-acid-based catalyst able to synthesize poly-L-lactic acid.
  • the organic-acid-based catalyst according to the present invention having a catalytic activity higher than those of conventional direct polymerization catalysts allows direct production of polylactic acid from lactic acid. Thus, use of it leads to simplification of the production process and improvement in productivity.
  • organic-acid-based catalyst according to the present invention can be reused. Thus, use of it also leads to cost reduction and also waste reduction.
  • FIG. 1 is a graph showing relationship between catalyst concentration and molecular weight.
  • FIG. 2 is a 1 H-NMR spectrum of a poly-L-lactic acid.
  • FIG. 3 is a GPC chromatogram.
  • FIG. 4 is a 1 H-NMR spectrum of a poly-L-lactic acid.
  • FIG. 5 is a 1 H-NMR spectrum of a L-lactic acid oligomer.
  • the organic-acid-based catalyst according to the present invention is an amine salt of sulfonic acid or a phosphine salt of sulfonic acid.
  • sulfonic acid in the present invention is used as a concept to include alkanesulfonic and arenesulfonic acids.
  • An alkanesulfonic acid is used favorably.
  • Those sulfonic acids are preferably substituted with fluorine atoms, and the number of substitution is preferably as large as possible.
  • use of a fluorine-substituted alkanesulfonic acid such as trifluoromethanesulfonic acid is the most preferable.
  • amine in the present invention is used as a concept to include aliphatic and/or aromatic primary, secondary, and tertiary amines, polyamines such as diamines and triamines etc. containing those amines, and nitrogen-containing heterocyclic compounds (monocyclic and fused rings).
  • the amine forming a salt with sulfonic acid is an alkylamine, an aromatic amine, or a nitrogen-containing heterocyclic compound, preferably an aromatic amine or a nitrogen-containing heterocyclic compound.
  • alkylamine examples include triethylamine, diethylcyclohexylamine, and the like; examples of the aromatic amine include aniline, diphenylamine and the like; and examples of the nitrogen-containing heterocyclic compound include pyridine, N-methylimidazole, and the like.
  • fluorine-substituted amines in particular, aromatic amines, are preferable, and the substitution number thereof is favorably as large as possible.
  • the fluorine-substituted aromatic amine is, for example, 2,3,4,5,6-pentafluoroaniline.
  • Examples of the phosphine forming a salt with sulfonic acid include monophosphines such as triarylphosphines, aryldialkylphosphines, diarylalkylphosphines and trialkylphosphines; diphosphines, triphosphines and others in combination thereof; and the like.
  • An aryl group-containing phosphine is preferable, and an example of such phosphines is triphenylphosphine.
  • the amine salt or phosphine salt of a sulfonic acid may be prepared by any known methods, but is generally prepared by adding an equivalent amount of a sulfonic acid to an amine or phosphine dissolved in an inert solvent such as methylene chloride dropwise while the mixture is cooled on ice, precipitating the salt by dilution with a salt-incompatible solvent such as ether, and collecting the precipitate by filtration.
  • the combination of the sulfonic acid and the amine or phosphine is adjusted so that the organic-acid-based catalyst according to the present invention has an acid dissociation constant (K) as high as possible.
  • K acid dissociation constant
  • Production of polylactic acid from lactic acid, which is fundamentally an esterification reaction, is carried out by azeotropic dehydration in the presence of an acid catalyst.
  • the organic-acid-based catalyst according to the present invention which provides proton ions (H + ) then as an acid catalyst, is lower in catalytic activity when its dissociation constant is excessively low.
  • L-lactic acid is normally available in a water-containing form.
  • Poly-L-lactic acid is prepared by dehydration condensation of such a lactic acid as above and a catalyst according to the present invention in a suitable solvent.
  • the catalyst according to the present invention is stable to water and can synthesize directly poly-L-lactic acid from L-lactic acid without through a step of forming a dimer or oligomer.
  • the concentration of the catalyst to lactic acid is normally in the range of 0.01 to 1 mol %.
  • the organic-acid-based catalyst according to the present invention has sufficiently high activity especially at a lower concentration of about 0.1 mol %.
  • the solvent is used for azeotropic removal of water generated in the dehydration condensation reaction.
  • the solvents for use include benzene, toluene, xylene and the like.
  • the amount is preferably about 1 to 3 times (by volume) larger than that of lactic acid, from the viewpoint of operational convenience.
  • the reaction temperature is preferably higher, but is the azeotropic temperature of the solvent, because azeotropic dehydration is needed.
  • benzene, toluene, and xylene which have an azeotropic temperature higher in that order, are more preferable in that order.
  • the maximum molecular weight of the polymer prepared seems to be dependent on the reaction temperature, and the polymerization is continued for the period until the molecular weight reaches the maximum value at the temperature.
  • the polymerization period is a condition to be determined properly according to desirable molecular weight, polymerization temperature, kind of catalyst and concentration of catalyst etc.
  • the catalyst according to the present. invention can produces a poly-L-lactic acid having a molecular weight (Mw) of approximately 10000 to 100000 without racemization of L-lactic acid by polymerization.
  • the organic-acid-based catalyst according to the present invention has been described by taking poly-L-lactic acid as an example, but can also be used in production of polyhydroxycarboxylic acids other than poly-L-lactic acid, such as those from D-lactic acid, DL-lactic acid, glycolic acid, mandelic acid, 2-hydroxyiso-valeric acid, 2-hydroxybutanoic acid, malic acid, tartaric acid, and amino acids, such as L-phenylalanine, glycine, and L- ⁇ -alanine; and production of copolymers thereof.
  • polyhydroxycarboxylic acids other than poly-L-lactic acid such as those from D-lactic acid, DL-lactic acid, glycolic acid, mandelic acid, 2-hydroxyiso-valeric acid, 2-hydroxybutanoic acid, malic acid, tartaric acid, and amino acids, such as L-phenylalanine, glycine, and L- ⁇ -alanine; and production of copolymers thereof.
  • the organic-acid-based catalyst according to the present invention is also usable when the polyhydroxycarboxylic acid is partially replaced with a polyvalent alcohol such as 1,4-butanediol, in particular, bivalent alcohol and/or a polyvalent carboxylic acid such as succinic acid, in particular, bivalent carboxylic acid or a lactone.
  • a polyvalent alcohol such as 1,4-butanediol
  • bivalent alcohol such as 1,4-butanediol
  • a polyvalent carboxylic acid such as succinic acid, in particular, bivalent carboxylic acid or a lactone.
  • the organic-acid-based catalyst according to the present invention can be reused. It is possible to recover the catalyst after polymerization, by diluting the reaction mixture with methanol, filtrating and separating the polymer obtained after precipitation, and removing the solvent from the filtrate. After removal of the solvent from the filtrate, the recovered catalyst may be used in the following reaction as it is or as needed after purification by recrystallization.
  • GPC gel-permeation chromatography
  • Measurement was performed by injecting 5 ⁇ l of the sample prepared by dissolving 40.0 mg of a polymer in 1.0 ml of THF.
  • the weight-average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) were calibrated by using polystyrene standard samples.
  • Trifluoromethanesulfonic acid product of TOKYO CHEMICAL INDUSTRY CO., LTD Pyridine: product of TOKYO CHEMICAL INDUSTRY CO., LTD N-Methylimidazole: product of TOKYO CHEMICAL INDUSTRY CO., LTD Triphenylphosphine: product of Wako Pure Chemical Industries, Ltd
  • triphenylphosphine 2.3 g was dissolved in 25 ml of methylene chloride in a 200-ml round-bottomed flask, and 0.9 ml of trifluoromethanesulfonic acid was added gradually dropwise while the mixture was agitated and cooled on ice.
  • the crystal obtained by precipitation from a solvent of methylene chloride/diethylether/hexane at 2/2/1 was suction-filtered and dried under reduced pressure. The yield was 78.9%
  • tin-based catalysts such as di-n-butyltin diacetate, di-n-butyltin oxide, Sn(II)2-ethylhexanoate or Sn(III) trifluoromethanesulfonate, or alternatively pyridinium p-toluenesulfonate is used, there was no polymer generated (molecular weight: up to approximately 500).
  • SnCl 2 gave an oligomer under the conditions of a catalyst/L-lactic acid ratio of 1.00 ⁇ 10 ⁇ 1 mol % and a reaction period of 22.5 hours. Elongation of the reaction period to 72 hours resulted in production of a polymer having a molecular weight of 9700.
  • the catalyst concentration is considered favorable in the range of 1.00 ⁇ 10 ⁇ 2 to 1.0 mol %.
  • Raised reaction temperature leads to increase in molecular weight of the polymer prepared at any catalyst concentration.
  • Results are shown in FIG. 2 .
  • the spectrum of an almost single methine proton indicates that there was no racemization occurring in the reaction.
  • the concentrated mother liquid was mixed with 4 ml of L-lactic acid and 8 ml of toluene, and the mixture was subjected to polymerization reaction similarly, to give a polymer having a weight-average molecular weight of 7400 at a yield of 64.6%.
  • the copolymer was isolated after polymerization by dissolving the polymer generated in CH 2 Cl 2 and reprecipitating it by addition of an excess amount of methanol. The precipitate obtained was suction-filtered and then dried under reduced pressure. Results are summarized in Table 5.
  • the following polymerization method was evaluated for improvement in molecular weight of the copolymer.
  • a mixture of L-lactic acid and a catalyst (PFPAT) (catalyst/monomer ratio: 1.00 ⁇ 10 ⁇ 1 mol %) was oligomerized in xylene for 24 hours by azeotropic dehydration. Then, L-phenylalanine was added in an amount of 10 mol % with respect to L-lactic acid, and the mixture was heated additionally for 22.5 hours.
  • the copolymer was isolated in a manner. similar to the preparation of the lactic acid-amino acid copolymer, to give a copolymer having Mw of 37200, Mw/Mn of 1.75 and monomer composition (LA/Phe) of 93/7 at a yield of 77.5%.
  • a mixture of glycolic acid (57 mol %) and a lactone (43 mol %) was allowed to react in the presence of a catalyst (TPPT: 0.1 mol %) in xylene at 160° C. for 24 hours, to give a copolymer.
  • the lactone used was ⁇ -caprolactone, ⁇ -valerolactone, or ⁇ -butyrolactone.
  • a mixture of succinic acid, a diol and glycolic acid at a molar ratio of 1.5:1.5:7 was allowed to react in the presence of catalyst (TPPT 0.1 mol %) in xylene at 160° C. for 24 hours, to give a copolymer.
  • a mixture of lactic acid and malic acid at a ratio of 90:10 (mol %) was allowed to react in the presence of a catalyst (TPPT 0.1 mol %) in toluene at 130° C. for 24 hours, to give a copolymer.
  • the yield was 31%, and the copolymerization ratio of the copolymer obtained, lactic acid:malic acid, was 90:10 (by molar ratio).

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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US12/308,066 2006-06-15 2007-06-12 Organic-acid-based catalyst for production of polylactic acid Abandoned US20090176963A1 (en)

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JP2006165991 2006-06-15
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Cited By (3)

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US20110065871A1 (en) * 2008-05-21 2011-03-17 Toray Industries, Inc. Method for producing aliphatic polyester resin, and an aliphatic polyester resin composition
WO2016071574A1 (en) 2014-11-06 2016-05-12 Teknologian Tutkimuskeskus Vtt Oy Method of producing glycolic acid polymers
CN114621179A (zh) * 2022-03-17 2022-06-14 中国神华煤制油化工有限公司 乙交酯的合成方法

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JP5387433B2 (ja) * 2009-02-13 2014-01-15 東レ株式会社 ポリ乳酸系樹脂の製造方法
FR2953523B1 (fr) * 2009-12-08 2013-02-15 Arkema France Procede de preparation d'un polymere d'au moins un monomere cyclique
JP5728781B2 (ja) * 2011-01-05 2015-06-03 国立大学法人京都工芸繊維大学 ラクチドの製造方法
WO2013133377A1 (ja) * 2012-03-08 2013-09-12 国立大学法人京都工芸繊維大学 ラクチドの製造方法
JP6509448B1 (ja) * 2017-07-04 2019-05-08 株式会社Ｊａｓｔ研究所 変性ポリ乳酸、高分子化された変性ポリ乳酸、並びにこれらの製造方法及び製造装置
WO2023282864A1 (en) * 2021-07-09 2023-01-12 Md Poli̇mer Gida Sanayi̇ Ti̇caret Li̇mi̇ted Şi̇rketi̇ Synthesis of poly(lactic acid) catalyzed by nanoparticle metal
WO2023076999A1 (en) 2021-10-28 2023-05-04 Exxonmobil Chemical Patents Inc. Thermoplastic polyester copolymer, preparation and use thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110065871A1 (en) * 2008-05-21 2011-03-17 Toray Industries, Inc. Method for producing aliphatic polyester resin, and an aliphatic polyester resin composition
US8173753B2 (en) 2008-05-21 2012-05-08 Toray Industries, Inc. Method for producing aliphatic polyester resin, and an aliphatic polyester resin composition
WO2016071574A1 (en) 2014-11-06 2016-05-12 Teknologian Tutkimuskeskus Vtt Oy Method of producing glycolic acid polymers
US10227446B2 (en) 2014-11-06 2019-03-12 Teknologian Tutkimuskeskus Vtt Oy Method of producing glycolic acid polymers
CN114621179A (zh) * 2022-03-17 2022-06-14 中国神华煤制油化工有限公司 乙交酯的合成方法

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EP2028209B1 (en) 2014-08-13
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EP2028209A1 (en) 2009-02-25
CN101466763B (zh) 2013-03-13
JP5264483B2 (ja) 2013-08-14
JPWO2007145195A1 (ja) 2009-10-29

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